CN112961985A - Fire recovery fine indium process for regenerating fine indium target by using target recovered material - Google Patents
Fire recovery fine indium process for regenerating fine indium target by using target recovered material Download PDFInfo
- Publication number
- CN112961985A CN112961985A CN202110137143.7A CN202110137143A CN112961985A CN 112961985 A CN112961985 A CN 112961985A CN 202110137143 A CN202110137143 A CN 202110137143A CN 112961985 A CN112961985 A CN 112961985A
- Authority
- CN
- China
- Prior art keywords
- indium
- heating
- target
- refined
- furnace
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
- C22B7/003—Dry processes only remelting, e.g. of chips, borings, turnings; apparatus used therefor
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/34—Electrolytic production, recovery or refining of metals by electrolysis of melts of metals not provided for in groups C25C3/02 - C25C3/32
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a pyrogenic process for recovering refined indium by using a target recovered material to regenerate a refined indium target. The pyrometallurgical recovery process of refined indium target material by using the target material recovered material shortens the granulation time of the recovered raw material, can effectively improve the reduction reaction efficiency, fully reacts, improves the purity of indium-tin alloy, avoids free pollution of metallic tin during electrolysis, and improves the efficiency and the purity of the recovered indium.
Description
Technical Field
The invention relates to the technical field of indium recovery, in particular to a pyrometallurgical recovery process for regenerating a refined indium target by using a target recovered material.
Background
Indium is a metal element and is widely used in the fields of aerospace, radio and electronic industries, medical treatment, national defense, high and new technology, energy and the like. The content of indium in the earth crust is 1 multiplied by 10 < -5 >%, although the indium also has independent minerals, the quantity of the indium is very small, and the indium mainly exists in pseudomorphic state in the wurtzite (the content of indium is 0.0001 percent to 0.1 percent), hematite, galena and other multi-metal sulfide ores. In addition, tin ore, wolframite and common amphibole also contain indium but the content is very low. Therefore, the recovery of scrap of the metal element indium is very important.
There are two methods for recovering indium: 1. wet recovery: after the indium-containing waste is subjected to treatment modes such as crushing and the like, soaking the indium-containing waste by acidic substances such as hydrochloric acid, sulfuric acid, nitric acid and the like to dissolve compounds such as indium oxide and the like in the indium-containing waste to form a salt solution of indium chloride, indium sulfate, indium nitrate and the like, adjusting proper acidity, replacing metal ions with activity lower than that of indium in the solution by metal indium through a crude indium impurity removal process, adjusting proper acidity, and replacing the metal indium by metals with stronger activity such as aluminum, zinc, magnesium and the like to form sponge indium; sponge indium is processed into a plate with a certain specification through the processes of washing, profiling, casting and the like, is placed into an electrolysis device to be used as an anode plate, is immersed into electrolyte, is introduced with voltage and current to enable indium ions to be dissociated from the anode plate, migrates to a cathode to precipitate indium simple substance to be stacked into a plate, then cathode indium is collected and cast into refined indium, and the refined indium is packaged and delivered after being detected to be qualified; the purity of indium obtained by this recovery method is not high, and it is necessary to increase the purity of indium by a plurality of electrolytic operations.
2. Alkali recovery: crushing an ITO target material, then crushing the crushed material to a granularity below 200 meshes, then adding the dried ITO target material powder into molten caustic soda, uniformly stirring the mixture, enhancing heat to enable the caustic soda to react with a tin compound in an ITO system to generate water-soluble sodium stannate, then washing the molten block after the reaction is cooled by using a large amount of tap water, collecting precipitates, adding acid to dissolve the precipitates, replacing indium or reducing the indium, and then electrolyzing the precipitates to generate refined indium. The recovery mode has certain limitation, namely the recovery mode is only suitable for systems such as ITO target materials, and the like, because the ITO target materials only contain tin elements except indium, and can react with caustic soda.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the process for recovering the refined indium by using the pyrogenic process of regenerating the refined indium target by using the target recovered material, so that the granulation time of the recovered raw material is shortened, the reduction reaction efficiency can be effectively improved, the reaction is full, the purity of the indium-tin alloy is improved, the free pollution of metal tin is avoided in electrolysis, and the efficiency and the purity of the recovered indium are improved.
In order to achieve the purpose, the invention adopts the technical scheme that: a fire recovery fine indium process for reproducing a fine indium target by using a target recovered material comprises the following steps:
1) a cleaning step, wherein leftover materials or residual targets of the target materials containing indium are recovered as indium recovered materials, the indium recovered materials are used as raw materials for reproducing refined indium, the selected indium recovered materials comprise more than 80 percent by weight of indium, 0 to 20 percent by weight of tin and the balance of impurities, the indium recovered materials are cleaned and dried,
2) a crushing step, namely crushing the dried indium reclaimed material by using a jaw crusher, controlling the particle size of crushed particles to be 2-3cm in the crushing process to obtain crushed particles with the average particle size of 2-3cm,
3) heating and reducing, namely putting the crushed particles into a heating and reducing furnace, vacuumizing the heating and reducing furnace, heating the temperature of the heating and reducing furnace to 800-1300 ℃, continuously introducing reducing gas, continuously decompressing the heating and reducing furnace to keep the gas pressure in the furnace below a limit, carrying out oxidation-reduction reaction on oxygen in the crushed particles and the reducing gas to generate gas and molten indium-tin alloy, stopping introducing gas and cutting off a power supply after the reaction is finished,
4) and an electrolysis step, namely pouring the indium-tin alloy into an anode plate mold, wherein the electrolytic liquid system is indium nitrate, and the cathode obtains refined indium with the indium content of more than 99.995%.
In a further technical scheme, the heating and reducing step comprises the following substep, 3.1) a step of placing the crushed particles into the heating and reducing furnace, wherein the stacking density of the crushed particles is set to 5500-.
In a further technical scheme, in the heating and reducing step, after the step of putting in, the method further comprises the following substeps of 3.2) vacuumizing the heating and reducing furnace, wherein the vacuum degree of the heating and reducing furnace is set to be 10-100Pa, 3.3) heating step, the temperature in the heating and reducing furnace is set to be 800-.
In a further technical scheme, in the electrolysis step, spongy metallic tin with the purity of more than 99% is left in the anode plate after electrolysis.
In a further technical scheme, in the electrolysis step, the current density is set to be 55-60A/m2The voltage is set at 0.18-0.22V.
In a further technical scheme, the indium reclaimed material comprises at least one of ITO target leftover materials, ITO residual targets or oxidized indium tin alloys.
In a further technical scheme, in the cleaning step, a solvent is used for cleaning and drying the surface of the indium reclaimed material.
In a further technical scheme, in the crushing step, the indium reclaimed materials are crushed by a jaw crusher, wherein the jaw crusher is provided with a fixed jaw plate and a movable jaw plate, the fixed jaw plate and the movable jaw plate are made of hard alloy materials, and the hardness of the hard alloy is greater than that of indium tin alloy.
In a further technical scheme, the Mohs hardness of the hard alloy materials of the fixed jaw plate and the movable jaw plate is more than 8 grade.
In a further technical scheme, in the heating reduction step, the reducing gas is selected from hydrogen, ammonia, methane or ethane, or the reducing gas is selected from a mixed gas formed by mixing one of hydrogen, ammonia, methane or ethane with an inert gas.
Compared with the prior art, the invention has the advantages that:
1. the crushing particles with the larger size of 2-3cm are selected for heating reduction, so that the crushing link is reduced, the energy is saved, the consumption is reduced, and the method is different from the crushing and grinding operation procedure commonly used in the indium recovery industry;
2. in the electrolysis step, a brand-new indium nitrate system is adopted for electrolysis, so that the free pollution of metal tin is avoided;
3. the equipment used in the process only needs to be invested once, and the equipment does not need to be frequently replaced due to the corrosion of acid and alkali and the like.
4. The process has simple procedures, small occupied area and less worker requirements, and is suitable for large-scale production;
5. the mode of feeding materials into the furnace completely and discharging the materials out of the furnace completely is adopted, namely the whole process is only contacted with gas, other impurity pollution cannot be additionally introduced, indium tin is conserved, and data statistics is facilitated;
6. except for the preparation of electrolyte, no chemical substances such as acid, alkali and the like which pollute the environment are used in the whole process of treating the indium-containing material, and no harmful substances are discharged, so that the method is green and environment-friendly.
Detailed Description
The following are merely preferred embodiments of the present invention, and do not limit the scope of the present invention.
A fire recovery fine indium process for reproducing a fine indium target by using a target recovered material comprises the following steps:
1) and a cleaning step, namely recovering the leftover materials or residual targets of the target materials containing indium as indium recovered materials, taking the indium recovered materials as raw materials for reproducing refined indium, selecting the indium recovered materials containing more than 80% of indium, 0-20% of tin and the balance of impurities by weight percent, cleaning and drying the indium recovered materials, and specifically, the indium recovered materials comprise at least one of ITO target leftover materials, ITO residual targets or oxidized indium tin alloys. Tap water is selected as the cleaning solvent. The indium reclaimed material is cleaned, so that the pollution of dust and the like on the surface of the indium reclaimed material is removed, and the cleanliness of the reclaimed raw material is improved.
2) And a crushing step, namely crushing the dried indium reclaimed materials by using a jaw crusher, controlling the particle size of the crushed particles to be 2-3cm in the crushing process to obtain crushed particles with the average particle size of 2-3cm, and specifically crushing the indium reclaimed materials by using the jaw crusher, wherein the jaw crusher is provided with a fixed jaw plate and a movable jaw plate, the fixed jaw plate and the movable jaw plate are made of hard alloy materials, and the hardness of the hard alloy is greater than that of indium-tin alloy. More specifically, the mohs hardness of the hard alloy material of the fixed jaw plate and the movable jaw plate is more than 8 grade. In the prior art, indium reclaimed materials are powdered and finally processed into millimeter or below sized particles. In the invention, the indium reclaimed material is crushed into crushed particles with larger particle size of 2-3cm, and the crushed particles have larger size, so that the crushing process is simple, the links of crushing and grinding the particles are reduced, the energy is saved, the consumption is reduced, and the method is different from the crushing and grinding operation procedures commonly used in the field, more importantly, after the crushed particles with larger size of 2-3cm are placed into a heating reduction furnace for accumulation, a larger void ratio is formed in an accumulation system of the crushed particles, so that the reducing gas can be fully mixed with the crushed particles, the efficiency of the reduction reaction is improved, and the reaction between the reducing gas and the crushed particles is more sufficient. Therefore, the crushed particles of 2 to 3cm produced in the crushing step serve to cushion the reaction efficiency and the reaction sufficiency of the subsequent heating reduction step.
3) And a heating reduction step, namely putting the crushed particles into a heating reduction furnace, vacuumizing the heating reduction furnace, heating the temperature of the heating reduction furnace to 800-1300 ℃, continuously introducing reducing gas, continuously decompressing the heating reduction furnace to keep the gas pressure in the furnace below a limit, carrying out oxidation reduction reaction on oxygen in the crushed particles and the reducing gas to generate gas and molten indium-tin alloy, and stopping introducing gas and cutting off a power supply after the reaction is finished to obtain the molten indium-tin alloy. In the step, reducing gas is introduced into the heating reduction furnace, the reducing gas and the crushed particles react at the set temperature in the heating reduction furnace, and molten indium tin alloy is obtained after the reaction is finished. Specifically, the method comprises the following substeps:
3.1) an introducing step of introducing the crushed particles into a heating-reducing furnace, the bulk density of the crushed particles being set at 5500-6000kg/m3The porosity formed by the accumulation of the crushed particles in the heating reduction furnace is set to be 16-26%, the crushed particles are accumulated to form gaps, and the width of the gaps between the crushed particles is controlled to be 1-5 mm; in the prior art, the recovered indium in the heating reduction step is even smaller in the order of millimeter-sized small particlesThe indium tin alloy powder is powdery, and the reduction gas cannot permeate the indium reclaimed material due to low porosity, so that the indium tin alloy formed by melting the indium reclaimed material wraps the unreacted indium reclaimed material, and the purity of the indium tin alloy obtained by heating and reducing is low. In the present invention, since crushed particles of 2 to 3cm having a relatively large size are obtained in the 2) crushing step, the crushed particles are charged into a heating and reducing furnace and piled to obtain a bulk density of 5500-6000kg/m3The stacking system with the porosity of 16-26% ensures that the broken particles have higher stacking density during reduction, can ensure that the stacking system has higher porosity while ensuring yield, has higher porosity in the stacking system, can keep the reducing gas to be fully contacted with each broken particle, ensures that the reducing gas and the broken particles react more fully, can prevent the phenomenon that indium tin alloy formed after small particles are melted wraps the broken particles in the prior art, and ensures that the purity of the obtained indium tin alloy after reduction reaction is higher.
3.2) vacuumizing, namely vacuumizing the heating and reducing furnace, wherein the vacuum degree of the heating and reducing furnace is set to be 10-100 Pa;
3.3) a heating step, namely setting the temperature in the heating and reducing furnace at 800-1300 ℃, heating the heating and reducing furnace before introducing gas to ensure that the temperature in the heating and reducing furnace reaches the reaction temperature of the crushed particles and the reducing gas, and enabling the reducing gas to quickly react with the crushed particles after introducing the gas to accelerate the initial reaction speed of the reducing gas and the crushed particles and prevent the reducing gas from insufficiently reacting with the crushed particles;
3.4) a reduction step, namely continuously introducing reducing gas into the heating and reducing furnace, reacting the crushed particles in the heating and reducing furnace with the reducing gas to generate gas and indium-tin alloy, and continuously releasing pressure to keep the air pressure in the heating and reducing furnace below the air pressure limit in the furnace; continuously reacting the reducing gas with the crushed particles at the temperature set by the heating and reducing furnace to continuously generate indium-tin alloy; introducing reducing gas into the heating and reducing furnace, and automatically relieving pressure when the gas pressure reaches the upper limit of the gas pressure in the heating and reducing furnace; specifically, the reducing gas is selected from hydrogen, ammonia, methane or ethane, or the reducing gas is selected from mixed gas formed by mixing one of hydrogen, ammonia, methane or ethane and inert gas; because the heating and reducing furnace has the upper limit of the gas pressure, the reducing gas is filled into the heating and reducing furnace, and simultaneously the reducing gas reacts with the crushed particles to generate gas, such as steam, carbon dioxide and the like, under the condition that the reducing gas is continuously introduced and the gas is generated in the reaction process, the gas pressure in the heating and reducing furnace is continuously increased, the gas pressure reaches the upper limit of the gas pressure in the heating and reducing furnace, the heating and reducing furnace automatically releases the pressure, and the gas pressure in the heating and reducing furnace is maintained below the upper limit of the gas pressure in the heating and reducing furnace;
3.5) a reaction ending step, continuously introducing reducing gas into the heating and reducing furnace, stopping generating gas in the heating and reducing furnace, and reducing the furnace temperature of the heating and reducing furnace to 160-250 ℃ to obtain molten indium-tin alloy. When no gas is generated in the heating and reducing furnace, which indicates that the reaction of the reducing gas and the broken particles is finished, the furnace temperature of the heating and reducing furnace is reduced to 160-250 ℃, and the indium-tin alloy is taken out, so that the taken-out indium-tin alloy is kept in a molten state.
In the prior art, the purity of the indium tin alloy obtained by the traditional process is 98.2%, but the purity of the indium tin alloy obtained by the process of the invention reaches 99.5%.
Taking the indium tin oxide reclaimed material with a 9010 proportion as an example, the price of the indium reclaimed material is about 60 percent of the price of refined indium in a raw material market at present, wherein the refined indium content is 74.4 percent, the actual recovery proportion is 74 percent calculated by the process recovery of 99.5 percent, the refined indium is recovered by 23.3 percent compared with the 60 percent of purchase cost, and the profit is considerable.
By combining the table 1.1 and the table 1.2, compared with the traditional refined indium target material preparation process, the average particle size of the crushed particles formed by crushing the indium reclaimed material is controlled to be 2-3cm, so that the process time required by preparing the refined indium target material is shortened by over 60-80%, the preparation speed is improved by over 2 times, the process is simplified, the production efficiency is higher, the electricity consumption is reduced by over 50%, the auxiliary material feeding cost in the refined indium preparation process is reduced by over 50%, and the overall process cost is reduced by over 50% compared with the traditional refined indium target material preparation process.
TABLE 1.1
Table 1.1 experimental comparison data obtained by crushing the indium reclaimed material to form crushed particles with different sizes in the crushing step, and setting the temperature of the heating reduction furnace at 1000 ℃ for reduction reaction in the heating reduction step. The data in the table is interpreted:
A. the size of the broken particles is 2-3cm, the size of the broken particles is relatively large, the breaking process is simple, the granulation time is short, the high stacking density and the high void ratio can be ensured, the effective void ratio is high, the width of gaps among the broken particles reaches 1-5mm, the gaps among the broken particles are large, the reducing gas can smoothly pass through the gaps among the broken particles and fully react with the broken particles, the reaction time is short, the reaction is full, the phenomenon that the generated indium-tin alloy wraps the broken particles is avoided, and the purity of the indium-tin alloy obtained by the reduction reaction is effectively improved.
B. In the first comparative example, since the crushed particle size is 0.3 to 0.4cm, the crushed particle size is small, resulting in a small bulk porosity, the length of the voids is in the range of 0.1 to 0.7mm, and the bulk density is 4000 to 4500kg/m3The method has the advantages that the porosity is low, the gap is small, the reducing gas cannot fully react with the broken particles, the broken particles and the reducing gas generate indium tin alloy, the indium tin alloy is in a flowing state at the reaction temperature, the flowing indium tin alloy wraps the unreacted broken particles to form indium tin alloy wrapping particles, the broken particles in the indium tin alloy wrapping particles cannot be reduced, the indium tin alloy wrapping particles flow with the indium tin alloy and enter the molten indium tin alloy obtained through the reduction reaction, and therefore the purity of the indium tin alloy is low.
C. In the second comparison scheme, because more ITO targets are planar, the size of the broken particles in the scheme is larger than that of the broken particles in the invention, the broken particles have more and larger planar binding surfaces, after the broken particles are stacked, the planar binding surfaces between the broken particles are mutually bound, so that reducing gas cannot smoothly pass through the binding surfaces mutually bound between the particles to form a large amount of entrainment, a large amount of broken particles cannot completely react, the yield of the indium-tin alloy obtained by reduction is greatly reduced, and the purity of the obtained indium-tin alloy is relatively lower than that of the scheme in the invention.
4) And an electrolysis step, namely pouring indium tin alloy into an anode plate die, wherein the electrolytic liquid is indium nitrate, the cathode obtains refined indium with the purity of more than 99.995%, and sponge-shaped metallic tin with the purity of more than 99% is left in the anode plate after electrolysis. Specifically, in the electrolysis step, the current density is set at 55-60A/m2And the voltage is set to be 0.18-0.22V, and the indium-tin alloy is electrolyzed. When the indium tin alloy is electrolyzed, if the electrolyte system is a sulfuric acid or hydrochloric acid system, the metal tin can be electrolyzed to enter the cathode, the purity of the indium obtained in the electrolysis step is reduced, multiple times of electrolysis are needed to obtain high-purity indium, and the electrolysis time is long. In the electrolysis step, indium nitrate is used as an electrolyte system, and metal tin cannot enter the nitric acid system of the electrolytic liquid in an ionic form, so that the metal tin cannot enter a cathode for deposition through electrolysis, the metal tin can be completely isolated from entering the electrolyte system, the purity of electrolytic refined indium can be effectively ensured, repeated electrolysis caused by improvement of indium purity can be effectively avoided, and the electrolysis time of the electrolysis step can be effectively shortened; meanwhile, the invention also realizes the high-purity separation of the metal indium and the metal tin, because the high-purity indium-tin alloy is obtained in the reduction step, and the current density is selected to be set to be 55-60A/m in combination with the electrolysis step of the invention2The voltage is set to be 0.18-0.22V, high-purity refined indium can be obtained only by electrolyzing the indium-tin alloy once, and high-yield high-purity metal indium can be obtained in a short time.
TABLE 1.2
Table 1.2 in the crushing step, the indium tin ratio was 90: the indium regrind of 10 is crushed to form crushed particles of varying sizes,in the heating reduction step, the temperature of the heating reduction furnace is set at 1000 ℃ for reduction reaction, and in the electrolysis step, the electrolysis density is 57A/m2And the voltage is 0.2V, the obtained indium tin alloy is electrolyzed for 120 hours, and experimental data are obtained.
Wherein, the comprehensive recovery rate in table 1.2 is the total weight of recovered refined indium divided by the theoretical indium content of the indium-containing material. After the indium reclaimed material is reduced, oxygen in the indium tin oxide reacts with reducing gas to form water vapor or carbon dioxide gas which is discharged, and indium tin alloy and a small amount of material slag which is not completely reduced are remained.
The data in the table is interpreted:
1. in the invention, because the size of the crushed particles of 2-3cm is selected, the higher stacking density can be ensured, and the more uniformly dispersed gaps can be ensured, because the gaps among the crushed particles are larger, the void ratio is high, the reducing gas can smoothly pass through the gaps among the crushed particles and fully react with the crushed particles, the reaction time is short, because the reaction is full and thorough, the phenomenon that the indium tin alloy obtained by the reduction reaction wraps the crushed particles is avoided, the purity of the indium tin alloy obtained by the reduction reaction is effectively improved, because the purity of the obtained indium tin alloy is higher, and because the indium nitrate is selected as an electrolyte system, the metal tin can not enter a nitric acid system of electrolytic liquid in an ion form, the metal tin can not enter a cathode for deposition, the metal tin can be completely isolated from entering the electrolyte system, and the purity of electrolytic refined indium can be effectively ensured, repeated electrolysis caused by improving the indium purity can be effectively avoided, and the electrolysis time of subsequent steps can be effectively shortened, so that the refined indium with high purity and high comprehensive recovery rate can be obtained in a short time.
2. In the first comparison scheme, due to the reason that the size of the broken particles is small, gaps among the broken particles are small, the passing flow of reducing gas is small, the local particles are wrapped, and the comprehensive recovery rate is low.
3. In the second comparison scheme, due to the fact that the size of the broken particles is too large, a large number of planes of the broken particles are attached to each other, reducing gas cannot effectively reach the whole surface of the broken particles, the reaction time is long, the energy consumption of the heating and reducing furnace and the consumption of the reducing gas are large, a large number of broken particles are completely wrapped by the indium tin alloy obtained through reaction to form half-cooked indium tin alloy, the yield of the indium tin alloy is low, the purity is low, and the comprehensive recovery rate is low.
The process for recovering refined indium has the following beneficial effects:
1. the size of the crushed particles is 2-3cm larger, so that the crushing link is reduced, the energy is saved, the consumption is reduced, and the method is different from the crushing and grinding operation procedure commonly used in the indium recovery industry;
2. in the electrolysis step, a brand-new indium nitrate system is adopted for electrolysis, so that the free pollution of metal tin is avoided;
3. the equipment used in the process only needs to be invested once, and the equipment does not need to be frequently replaced due to the corrosion of acid and alkali and the like, so that the production cost is low.
4. The process has simple procedures, small occupied area and less worker requirements, and is suitable for large-scale production;
5. the mode of feeding materials into the furnace completely and discharging the materials out of the furnace completely is adopted, namely the whole process is only contacted with gas, other impurity pollution cannot be additionally introduced, indium tin is conserved, and data statistics is facilitated;
the concrete expression is as follows: in the steps of 1) cleaning and 2) crushing, impurities cannot be mixed into the indium reclaimed materials or adhered to the surfaces of the indium reclaimed materials, and the cleanliness of the indium reclaimed materials before being placed into a heating and reducing furnace is maintained;
in 3) the heating reduction step, directly add indium reclaimed materials in the heating reduction furnace once only and carry out redox reaction, only need to heat indium reclaimed materials and let in reducing gas can, need not to mix other reactants such as other likepowder, the reaction raw materials are few and reaction conditions are simple, and the reaction between the reactant is abundant, the reaction obtains high-purity indium tin alloy, gas and vapor, gas or vapor discharge when the pressure release, the high-purity indium tin alloy that the reaction obtained leaves, the resultant need not to establish the separation step in addition, avoid mixing impurity in the separation, easy operation.
In the step 4) of electrolysis, because indium nitrate is adopted as an electrolyte system, metal tin cannot enter the nitric acid electrolyte system in an ionic form, and therefore metal tin cannot enter a cathode for deposition, the separation of metal indium and metal tin is effectively realized, and the purity of point-resolved indium is effectively improved.
In the whole process, the cleanliness of the raw materials is kept in the treatment of the raw materials, then the raw materials are subjected to oxidation-reduction reaction, the quantity of reactants is controlled to be small, the reaction process automatically realizes the automatic high-purity separation of liquid and gas, and mutual pollution between metal tin and metal indium is prevented in the electrolysis step, so that the purposes of full-in and full-out and convenience in data statistics are achieved.
6. Except for the preparation of electrolyte, no chemical substances such as acid, alkali and the like which pollute the environment are used in the whole process of treating the indium-containing material, and no harmful substances are discharged, so that the method is green and environment-friendly.
The above description is only a preferred embodiment of the present invention, and for those skilled in the art, the present invention should not be limited by the description of the present invention, which should be interpreted as a limitation.
Claims (10)
1. A fire recovery fine indium process for reproducing a fine indium target by using a target recovered material is characterized by comprising the following steps of: comprises the following steps of (a) carrying out,
1) a cleaning step, wherein leftover materials or residual targets of the target materials containing indium are recovered as indium recovered materials, the indium recovered materials are used as raw materials for reproducing refined indium, the selected indium recovered materials comprise more than 80 percent by weight of indium, 0 to 20 percent by weight of tin and the balance of impurities, the indium recovered materials are cleaned and dried,
2) a crushing step, namely crushing the dried indium reclaimed material by using a jaw crusher, controlling the particle size of crushed particles to be 2-3cm in the crushing process to obtain crushed particles with the average particle size of 2-3cm,
3) heating and reducing, namely putting the crushed particles into a heating and reducing furnace, vacuumizing the heating and reducing furnace, heating the temperature of the heating and reducing furnace to 800-1300 ℃, continuously introducing reducing gas, continuously decompressing the heating and reducing furnace to keep the gas pressure in the furnace below a limit, carrying out oxidation-reduction reaction on oxygen in the crushed particles and the reducing gas to generate gas and molten indium-tin alloy, stopping introducing gas and cutting off a power supply after the reaction is finished,
4) and an electrolysis step, namely pouring the indium-tin alloy into an anode plate mold, wherein the electrolytic liquid system is indium nitrate, and the cathode obtains refined indium with the indium content of more than 99.995%.
2. The pyrometallurgical refined indium recovery process by using a target recycled material to reconstruct a refined indium target according to claim 1, which is characterized in that: in the heating reduction step, the following sub-steps are included,
3.1) a step of placing the crushed particles in the heating-reducing furnace, the bulk density of the crushed particles being set at 5500-6000kg/m3The porosity of the crushed particles accumulated in the heating and reducing furnace is set to 16-26%, and the gap width between the crushed particles is controlled to 1-5 mm.
3. The pyrometallurgical refined indium recovery process using recycled target material to recreate refined indium target according to claim 2, wherein: in the heating reduction step, after the putting step, the substep of,
3.2) a vacuumizing step, vacuumizing the heating and reducing furnace, wherein the vacuum degree of the heating and reducing furnace is set to be 10-100Pa,
3.3) a heating step, setting the temperature in the heating reduction furnace at 800-,
3.4) a reduction step, namely, continuously introducing the reducing gas into the heating reduction furnace, reacting the crushed particles in the heating reduction furnace with the reducing gas to generate gas and indium-tin alloy, continuously releasing pressure to keep the air pressure in the heating reduction furnace below the air pressure limit in the furnace,
3.5) a reaction ending step, stopping generating gas in the heating and reducing furnace, and reducing the furnace temperature of the heating and reducing furnace to 160-250 ℃ to obtain molten indium-tin alloy.
4. The pyrometallurgical refined indium recovery process by using a target recycled material to reconstruct a refined indium target according to claim 1, which is characterized in that: in the electrolysis step, spongy metallic tin with purity of more than 99% is left in the anode plate after electrolysis.
5. The pyrometallurgical refined indium recovery process by using a target recycled material to reconstruct a refined indium target according to claim 1, which is characterized in that: in the electrolysis step, the current density is set at 55-60A/m2The voltage is set at 0.18-0.22V.
6. The pyrometallurgical refined indium recovery process by using a target recycled material to reconstruct a refined indium target according to claim 1, which is characterized in that: the indium reclaimed material comprises at least one of ITO target leftover materials, ITO residual targets or oxidized indium tin alloys.
7. The pyrometallurgical refined indium recovery process by using a target recycled material to reconstruct a refined indium target according to claim 1, which is characterized in that: and in the cleaning step, a solvent is used for cleaning the surface of the indium reclaimed material and then drying the cleaned surface.
8. The pyrometallurgical refined indium recovery process by using a target recycled material to reconstruct a refined indium target according to claim 1, which is characterized in that: in the crushing step, the jaw crusher is provided with a fixed jaw plate and a movable jaw plate, the fixed jaw plate and the movable jaw plate are made of hard alloy, and the hardness of the hard alloy is greater than that of indium-tin alloy.
9. The process for recovering refined indium by using the pyrometallurgy for reconstructing refined indium target material by using the recovered target material according to claim 8, wherein: the Mohs hardness of the hard alloy materials of the fixed jaw plate and the movable jaw plate is more than 8 grade.
10. The pyrometallurgical refined indium recovery process by using a target recycled material to reconstruct a refined indium target according to claim 1, which is characterized in that: in the heating reduction step, the reducing gas is selected from hydrogen, ammonia gas, methane or ethane, or the reducing gas is selected from mixed gas formed by mixing one of hydrogen, ammonia gas, methane or ethane and inert gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110137143.7A CN112961985B (en) | 2021-02-01 | 2021-02-01 | Fire recovery process for recovering refined indium from target material recovered material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110137143.7A CN112961985B (en) | 2021-02-01 | 2021-02-01 | Fire recovery process for recovering refined indium from target material recovered material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112961985A true CN112961985A (en) | 2021-06-15 |
| CN112961985B CN112961985B (en) | 2023-06-13 |
Family
ID=76272685
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110137143.7A Active CN112961985B (en) | 2021-02-01 | 2021-02-01 | Fire recovery process for recovering refined indium from target material recovered material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112961985B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201139693A (en) * | 2009-12-10 | 2011-11-16 | Tosoh Corp | Method for producing metal indium and molten salt electrolytic bath |
| CN104818388A (en) * | 2015-05-06 | 2015-08-05 | 昆明鼎邦科技有限公司 | Method of vacuum-reducing separating indium from tin from an In/Sn oxide |
| CN105420756A (en) * | 2015-12-08 | 2016-03-23 | 南京中锗科技有限责任公司 | Method for recycling indium from waste ITO target material through reduction method |
| CN110498443A (en) * | 2019-08-23 | 2019-11-26 | 云南锡业集团（控股）有限责任公司研发中心 | A method of with ITO give up target recasting ITO powder |
-
2021
- 2021-02-01 CN CN202110137143.7A patent/CN112961985B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201139693A (en) * | 2009-12-10 | 2011-11-16 | Tosoh Corp | Method for producing metal indium and molten salt electrolytic bath |
| CN104818388A (en) * | 2015-05-06 | 2015-08-05 | 昆明鼎邦科技有限公司 | Method of vacuum-reducing separating indium from tin from an In/Sn oxide |
| CN105420756A (en) * | 2015-12-08 | 2016-03-23 | 南京中锗科技有限责任公司 | Method for recycling indium from waste ITO target material through reduction method |
| CN110498443A (en) * | 2019-08-23 | 2019-11-26 | 云南锡业集团（控股）有限责任公司研发中心 | A method of with ITO give up target recasting ITO powder |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112961985B (en) | 2023-06-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10519556B2 (en) | Process for recycling waste carbide | |
| CN101289712B (en) | Process for recovering indium from indium-containing material | |
| CN110527835B (en) | Method for recycling soft package full components of waste ternary lithium battery | |
| CN104831064B (en) | Acidleach-cyclone electrolytic cell technology technique of high efficiente callback copper from lead copper matte is pressed with oxygen | |
| KR101497921B1 (en) | Recycling methdo of ncm type cathode active material from waste lithium ion battery and ncm type cathode active material recycled by the same | |
| CN104818388B (en) | A kind of indium tin oxide vacuum reduction separating indium and the method for stannum | |
| CN112079369B (en) | Method for preferentially extracting lithium and cooperatively recovering manganese from waste lithium ion battery | |
| CN103911514B (en) | The recovery and treatment method of scrap hard alloy grinding material | |
| CN111187924B (en) | Continuous lithium smelting device and method for lithium-containing material | |
| JP5913639B2 (en) | Method for producing indium oxide-tin oxide powder, method for producing ITO target, and method for producing indium hydroxide-metastannic acid mixture | |
| Li et al. | A review on the extraction and recovery of critical metals using molten salt electrolysis | |
| Sheng et al. | Preparation of electronic grade manganese sulfate from leaching solution of ferromanganese slag | |
| CN113387387A (en) | Method for preparing sodium tungstate solution by utilizing tungsten-containing waste in short process | |
| CN108330276A (en) | Method for preparing high-purity iron powder using iron vitriol slag and products thereof and application | |
| CN102634819A (en) | Method for preparing electrolytic manganese/electrolytic manganese dioxide through leaching manganese oxide by sulfur dioxide | |
| CN112961985B (en) | Fire recovery process for recovering refined indium from target material recovered material | |
| CN116995327A (en) | Method for recycling lithium from ternary positive electrode waste | |
| JP6172526B2 (en) | Adjustment method of copper concentration of chlorine leachate in nickel chlorine leaching process | |
| CN104233372B (en) | Method for recovering copper from lead matte | |
| Su et al. | Reduction mechanism of spent ITO target in CaCl2 molten salt | |
| CN114875240A (en) | Method for treating copper-cobalt alloy of waste lithium battery and application | |
| JP6362029B2 (en) | Nickel sulfide raw material processing method | |
| CN113718268A (en) | Method for recycling tungsten waste | |
| CN102677098A (en) | Method for preparing rich cerium misch metal | |
| CN111364060B (en) | Method for producing pure silver and co-producing metal aluminum from waste silver catalyst with alumina as carrier |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |